Astringent compositions

ABSTRACT

THE PRESENT INVENTION IS CONCERNED WITH AEROSOL SPRAY ANTI-PERSPIRANT COMPOSITIONS OF THE TYPE IN WHICH THE ASTRINGENT MATERIAL IS SUSPENDED AS A SOLID IN AN ANHYDROUS LIQUID VEHICLE AND DISPENSED IN THIS FORM AND MORE PARTICULARYL WITH ANTI-PERSPIRANT COMPOSITIONS OF THIS TYPE WHICH HAVE SUBSTANTIALLY REDUCED PROPENSITY TO STAIN CLOTHING. GENERALLY SUCH IMPROVEMENTS ARE BROUGHT ABOUT BY USING AS THE LIQUID VEHICLE FOR SUCH COMPOSITIONS ESTERS WHICH ARE MISCIBLE WITH THE PROPELLANT AND WHICH ARE FORMED FROM TRI-BASIC ACIDS AND LOWER ALIPHATIC ALCOHOLS.

United States Patent Oflice 3,833,721 ASTRINGENT COMPOSITIONS Robert E.Saute, Los Angeles, Calif., and Bernard Siegal, Bedford, Mass.,assignors to The Gillette Company, Boston, Mass. N Drawing. Filed July14, 1972, Ser. No. 272,044 Int. Cl. A61k 7/00 U.S. Cl. 424-47 9 ClaimsABSTRACT OF THE DISCLOSURE The present invention is concerned withaerosol spray anti-perspirant compositions of the type in which theastringent material is suspended as a solid in an anhydrous liquidvehicle and dispensed in this form and more particularly withanti-perspirant compositions of this type which have substantiallyreduced propensity to stain clothing. Generally such improvements arebrought about by using as the liquid vehicle for such compositionsesters which are miscible with the propellant and which are formed fromtri-basic acids and lower aliphatic alcohols.

Aerosol anti-perspirant compositions in which the astringent material,e.g. aluminum chlorhydroxide, is dispensed as a solid suspended in ananhydrous hydrophobic liquid vehicle such as mineral oil, isopropylmyristate or isopropyl palmitate have been widely marketed. Althoughsuch compositions are effective in reducing perspiration they have atendency to impart stains to clothing which (stains) remain subsequentto laundering. The present invention is concerned with providinganti-perspirant compositions of this type which have substantiallyreduced tendency to stain clothing.

It has been found in the present invention that the staining due to suchcompositions can be substantially reduced by using as the liquid vehiclefor said compositions an ester which is miscible with the propellant andwhich is selected from the group represented by the formula:

wherein R is a hydrogen atom or a 2 to 3 carbon acyl group, i.e. anacetyl or a propionyl group and each R is the same or different than theother R s and is an alkyl radical comprising less than 4 carbon atoms.In especially preferred embodiments of the present invention, each R isan ethyl radical. As examples of compounds within the above formula,mention may be made of triethylcitrate and acetyl triethylcitrate.Especially good results have been obtained with triethylcitrate whichhas been found to be particularly non-toxic, non-irritating andnon-corrosive, has good stability in the compositions and in certaininstances actually enhances the fragrance of the perfumes used therein.

It should be understood that when desired, if R is a hydrogen, thehydroxy group may be alkoxylated by a 1 to 3 carbon alkyl group or thealkyl radicals (R may be further substituted by hydroxy or 1 to 2 carbonalkoxy groups provided that the esters remain miscible with thepropellant and the number of carbon atoms is commensurate with that setforth above.

Generally the astringent may be selected from any of the materials ofthis nature which are available, e.g. aluminum sulfate, aluminumchloride, aluminum chlorhydroxides such as Al(OH) Cl and Al OH Claluminum sulfocarbolate, zinc chloride, zinc sulfocarbolate, zincsulfate, zirconium oxychloride, sodium zirconium lactate, sodiumzirconium glycolate, zirconyl hydroxy chloride, zirconium sulfate,physical mixtures of the above, and mixed compounds and complexescomprising 2 or more of the 3,833,721 Patented Sept. 3, 1974 abovecations such as a mixed aluminum zirconium chlorhydroxide complex. Thepreferred astringents for use in the composition of this invention arethe aluminum chlorhydroxides. The amount of astringent employed may bevaried but in most compositions it will be present in amounts rangingbetween about 0.5% to about 10% by weight of the total compositionincluding the propellant. In preferred compositions, it will be presentin amounts ranging between about 1 to about 7.5%. Further the astringentshould be finely ground in order to prevent the valve from clogging.Usually if the particle size is less than 100 microns and preferablyless than 60 microns, clogging will be held to a minimum.

The ester is present in amounts such that in combination with thepropellant it will be the continuous phase of the dispersion orsuspension. As can be appreciated, this amount will vary depending uponthe amount of astringent employed. In most instances, the ester willcomprise from about 0.5 to about 50% by weight of the total compositionincluding the propellant. In preferred compositions, the ester ispresent in amounts ranging between about 0.5 to about 15%.

Generally any of the materials which have been employed as propellantsin aerosol compositions may be used in the compositions of the presentinvention; provided of course that they are miscible with the liquidvehicle. As examples of such materials mention may be made of:dichloroditluoromethane, trichloromonofluoromethane,trichlorotrifiuoroethane, tetrafiuorodichloroethane, butane, propane,isobutane and mixtures and blends of the above. The propellant willgenerally be present in amounts which will be sufiicient to dispense allof the composition at a moderate velocity. In most instances thecompositions will have vapor pressures ranging between 15 and 85p.s.i.g. and preferably between 20 and 40-. Generally the propellantwill be present in amounts varying between 50 to 98% by weight of thetotal composition and preferably between to 98%.

The preferred compositions of the present invention will further includea suspending, dispersing or flocculating agent to prevent the astringentfrom agglomerating or settling. As examples of such agents, mention maybe made of clays, such as bentonite, modified clays, e.g. the reactionproduct of bentonite and a surface active quaternary salt, silicas suchas colloidal silicon dioxide, silicates, polymeric suspending agentssuch as cellulose and derivates thereof and surfactants such as highmolecular weight amides, e.g. lauryl monoethanolamide. If desired, thecompositions may further include other ingredients such as perfumes,emollients, talc, starches, anti-bacterials, etc.

The effectiveness of the compositions of the present invention inreducing stain was demonstrated by using the esters disclosed herein ona weight basis in place of isopropyl palmitate in a standard formula andmeasuring the extent of staining it caused as compared with thecomposition containing isopropyl palmitate. The standard formula was asfollows:

Percent by weight Vehicle 6.12 I-Iexachlorophene 0.04 AluminumChlorohydroxide 3.40 Pyrogenic Colloidal Silica 0.35 Perfume 0.35

(2) Reflectance readings were taken on virgin, unused, unlaunderedmaterial using a Photovolt Model 670 Reflectometer equipped with a 610-Tsearch unit and a green filter. The average of 12 readings wasdesignated as R (3) The swatches were laundered in an apartment sizewasher for 15 minutes in 10 liters of hot (about 55 C.) tap watercontaining 30 g. of an alkyl aryl sulfonate detergent and 100 ml. of acommercial hypochlorite bleach. The swatches were rinsed for two 10minute cycles in hot tap water and then for a 10 minute cycle in cooldistilled water. The swatches were dried for 24 hours at 60 C. in a 220volt Freas Model 625 forced draft oven.

(4) Five swatches of the fabric were mounted on poster boards and thecenter portions of each were subjected to three 2-second sprays of theformulation which was being tested. An average of about six grams of theformulation was dispensed over the 6-second period. The swatches wereallowed to stand for 30 minutes and then smeared with a spatula to evenout irregularities in the application area.

(5) The swatches were laundered and dried in the same manner as setforth in step 3 above.

(6) The Photovolt Refiectometer was warmed up for 30 minutes and threereadings were made of the stained area. The cloth was rotated 90 andthree additional readings were made. The average of the six readings inthe stained area was referred to as R (7) Three reflectance readingswere taken in the edge or non-stained areas and the cloth was rotated 90and three additional readings were taken. The average of six readings inthe non-stain area were referred to as R (8) The Stain Index wascalculated for each formulation after each cycle by using the followingequation:

Stain Index=l00 TABLE L-STAIN INDICES Triethyl citrate (TEC) vs.isopropyl palmitate (IPP) Staining cycle Test number 4 5 6 Average 1'IEC 0 IPP 58. 5 60.70

2 TEC 0.5 0.2 IPP 62.0 63.5

3 'IEC 18.5 22.5 IPP 70.5 71.8

4 TEC 19.5 20.3 IPP 47.0 46.0

5 TEC 21.5 20.5 IPP 50.0 51.8

No'rE.Grand average stain indices, 5 tests, 13 cyclesTEC, 11.5;

IPP, 60.3.

As can be noted, the triethyl citrate has substantially lower stainindiccs than the isopropyl palmitate.

Table II summarizes the results of a test in which acetyltriethylcitrate was run against isopropyl palmitate.

TABLE II.STAIN INDICES Acetyl triethylcitrate vs. isopropyl palmitate(IPP) The effectiveness of the esters of the present invention inreducing stain in viva was demonstrated in a test wherein:

(1) About males were given coded cans of antiperspirants containingparallel triethyl citrate and isopropyl palmitate formulations and newcotton T-shirts. They were instructed to use one product under the rightaxilla only and the other under the left axilla only. The T-shirt was tobe worn for at least four cycles of home laundry. After four weeks, theT-shirts were collected (86 men responded) and evaluated. The T-shirt,underarm areas in contact with the axilla under which triethyl citratewas used consistently showed substantially less stain than that underwhich isopropyl palmitate had been used. This observation wassignificant at greater than a 99.5% confidence level.

A similar test was performed on 22 men to whom the formulations wereapplied by an observer, who then laundered the T-shirts en masse. Afterfour and six cycles of application, use, and laundry, the triethylcitrate side of the T-shirt again showed substantially less stainingthan the isopropyl palmitate side at a confidence level greater than99.5%.

In a further test, the triethyl citrate formulation was tested alongwith an isopropyl palmitate control composition on twenty differentsynthetic and natural fibers for 1 cycle of the above mentioned staintest. On only one type material (diacetate) was the citrate formulationfound to cause more stain than the control.

Having thus described the invention what is claimed is:

1. An aerosol astringent composition having improved antistainproperties, said composition comprising 0.5% to 10% by weight of anastringent material selected from the group consisting of aluminumsulfate, aluminum chloride, aluminum chlorohydroxide, aluminumsulfocarbolate, zinc chloride, zinc sulfocarbolate, zinc sulfate,zirconium oxychloride, sodium zirconium lactate, sodium zirconiumglycolate, zirconyl hydroxy chloride, zirconium sulfate and aluminumzirconium chlorohydroxide complex, 50 to 98% by weight of a propellantselected from the group consisting of dichlorodifluoromethane,trichloromonofluoromethane, trichlorotrifiuorethane,tetraflurodichloroethane, butane, propane, isobutane and mixtures andblends thereof and 0.5 to 50% by weight of a vehicle, said astringentmaterial being insoluble in both said propellant and said vehicle andsaid vehicle being miscible with the propellant and being represented bythe formula:

CHzCOOR RO COOR CHQCOOR;

wherein R is a hydrogen atom or a 2 to 3 carbon acyl group and each Rmay be the same or different than the other Rfs and is an alkyl radicalcomprising less than 4 carbon atoms, said percentages are based onweight of the total composition. 1

2. A composition as defined in claim 1 wherein each R is an ethyl group.

3. A composition as defined in claim 1 wherein R is a hydrogen atom.

4. A composition as defined in claim 1 wherein R is an acetyl group.

5. A composition as defined in claim 1 wherein said astringent materialis aluminum chlorhydroxide.

5 6 6. A composition as defined in claim 1 wherein said 3,030,274 4/1962Grant 424--68 X vehicle is triethyl citrate. 3,544,258 12/1970 Presantet a1. 4244-47 7. A composition as defined in claim 6 wherein said3,634,480 1/1972 Sheffield 42447 astringent material is aluminumchlorhydroxide.

8. A composition as defined in claim 1 wherein said 5 OTHER REFERENCESvehicle is acety1triethy1citrate de Navarre International Encyclopediaof Cosmetic 9. A composition as defined in claim 8 wherein said MammalTrade Names, 1957, PP- 334 and astringent material is aluminumchlorhydroxide.

ALBERT T. MEYERS, Primary Examiner References Cited 10 D. R. ORE,Assistant Examiner UNITED STATES PATENTS 3,721,693 3/1973 Fein et al.424-47 2,210,014 8/1940 Teller 424-68

